Lec:15

9th APRIL,2018

DEPARTMENT OF MECHANICAL ENGINEERING

ME- 1413: Engineering
Materials
• Syed Hassan Shah
• Assistant Professor
• Department of Mechanical
Engineering
LAST TIME!
• COLD WORKING
• Bauschinger effect
• THERMAL PROPERTIES OF MATERIALS
TODAY’S TOPIC
 Thermal Expansion
Materials change size when temperature
is changed
Tinitial
 initial
Tfinal > Tinitial
Tfinal
 final

final  initial
 α(Tfinal  Tinitial )
initial
linear coefficient of
thermal expansion (1/K or 1/°C)

5
 Thermal Expansion
• If the curve is not symmetric, the average position in
which the atom sits shifts with temperature.
• Bond lengths therefore change (usually get bigger for
increased T).
• Thermal expansion coefficient is nonzero.

Bond energy
r(T1)
r(T5)

Bond length (r)

increasing T

T5
bond energy vs bond length
curve is “asymmetric”
T1
 THERMAL EXPANSION: COMPARISON
 (10-6/K) •Thermal expansion
Material
• Polymers at room T mismatch is a major
Polypropylene 145-180 problem for design of
Polyethylene 106-198
Polystyrene 90-150 everything from
Teflon 126-216 semiconductors to
• Metals
bridges.
increasing 

Aluminum 23.6
Steel 12
Tungsten 4.5
•Particularly an issue
Gold 14.2 in applications where
• Ceramics temperature changes
Magnesia (MgO) 13.5
Alumina (Al2O3) 7.6 greatly (esp. engines).
Soda-lime glass 9 Why does  generally
Silica (cryst. SiO2) 0.4
decrease with increasing
bond energy?
Selected values from Table 19.1, Callister 6e.
 Thermal Shock Resistance For Brittle
materials e.g
• Occurs due to: nonuniform heating/cooling ceramics
• Ex: Assume top thin layer is rapidly cooled from T1 to T2
rapid quench
s
tries to contract during cooling T2 Tension develops at surface
resists contraction T1 s  E l (T1 T2 )
Temperature difference that Critical temperature difference
can be produced by cooling: for fracture (set s = sf)
quench rate sf
(T1  T2 )   (T1 T2 ) fracture 
k E l
set equal
sf k
• (quench rate) for fracture  Thermal
Shock Resistance (TSR)  E l
sf k
• Large TSR when is large
E l
Numerical example important 12
These all are members of ceramic material
They belong to Amorphous Type.
E – Young’s Modulus
v = poisson ratio
α = Thermal expansion Coefficient
 Thermal
• Application:
Protection System
Re-entry T
Space Shuttle Orbiter Distribution

reinf C-C silica tiles nylon felt, silicon rubber

(1650°C) (400-1260°C) coating (400°C)

(400-1260C):
• Silica tiles
-- large scale application -- microstructure:
~90% porosity!
Si fibers
bonded to one
another during
heat treatment.
100 mm

25
 Linear polymer - Any polymer in which molecules are in the form
of spaghetti-like chains.
 Thermoplastics - Linear or branched polymers in which chains of
molecules are not interconnected to one another.
 Thermosetting polymers - Polymers that are heavily cross-linked
to produce a strong three dimensional network structure.
 Elastomers - These are polymers (thermoplastics or lightly cross-
linked thermosets) that have an elastic deformation > 200%.
SUMMARY
 Diffusion
Diffusion Mass transport by atomic motion. Diffusion is
a consequence of the constant thermal motion of
atoms, molecules and particles that results in
material moving from areas of high to low
concentration-.
Mechanisms
• Brownian motion is the seemingly random
movement of particles suspended in a liquid or gas.
• Solids – vacancy diffusion or interstitial diffusion.

35
We need a way of splitting up the Gibbs free energy of a phase among the various
components of the phase--how does the Gibbs free energy of a phase vary with
composition--We address these issues by defining a partial Gibbs free energy for each
component at constant pressure and temperature and constant composition of other
components, called the partial molar Gibbs free energy or chemical potential
A partial molar property is a thermodynamic
quantity which indicates how an extensive
property of a solution or mixture varies with
changes in the molar composition of the mixture
at constant temperature and pressure
 Diffusion Mechanism
Vacancy diffusion

Interstitial diffusion

45
 Activation Energy
G  H  TS
G Vibration frequency: 
Energy

Nearest neighbor sites: z

Atom position
Jump Frequency :

Interstitial diffusion Vacancy diffusion

 Gm 
Gm  H m  TS m   zX V v exp  
 RT 
H m  TS m



 H m 
D  D0 exp  
 RT  46
 Vacancy Diffusion
• Applies to substitutional impurities
• Atoms must hop to open vacancy
• Rate depends on probability of overcoming migration activation
energy, Qm
pQ = Bexp(-Hm/kT)
And
• Probability of a vacancy
pv = Nv/N = exp(-Hv/kT)
• Here is Diffusion Coefficient is:
D = D0 exp(-Hd/kT)
where Hd = Hm + Hv
48
 Interstitial Diffusion

• Applies to interstitial impurities (tend to be low concentration)

• Most interstitial sites are not occupied
• More rapid than vacancy diffusion
• Activation energy involves overcoming the migration activation
energy, Hm.
• Rate is defined by the Diffusion Coefficient
D = D0exp(-Hd/kT)

where D0 is a pre-exponential
factor (m2/s) and Hd = Hm

51
 Data
Interstitial diffusion in Fe Self-diffusion data for metals

solute Hm(kJmol-1) D0(10-6m2s-1) metal Tm(K Q D0 (10- D(Tm)

) (kJmol-1) ms )
6 2 -1
(10-12m2s-1)
C 84 2.0
Al 933 142 170 1.9
N 76 0.3
Cu 1356 200 31 0.59
H 13 0.1
Ni 1726 279 190 0.65
-Fe 1805 284 49 0.29

isotope

x=0

52
Other Diffusion Mechanisms

Direct exchange

Zener ring
53
 LAW’S OF DIFFUSION
Adolf Eugen Fick was a German-born physician
 Fick’s first law - The equation relating the flux of atoms by
diffusion to the diffusion coefficient and the concentration
©2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning™ is a trademark used herein under license.

gradient.
 Diffusion coefficient (D) - A temperature-dependent coefficient
related to the rate at which atoms, ions, or other species diffuse.
 Concentration gradient - The rate of change of composition with
distance in a nonuniform material, typically expressed as
atoms/cm3.cm or at%/cm.
©2003 Brooks/Cole, a division of Thomson Learning, Inc.
Thomson Learning™ is a trademark used herein under
license.
DIFFUSION FLUX
 Non-steady State Diffusion
• The concentration of diffusing species is a function of both time and
position C = C(x,t)
• In this case Fick’s Second Law is used
 Fick’s second law - The partial differential equation that describes
the rate at which atoms are redistributed in a material by diffusion.
Fick’s Second Law C  2C
 D 2
t x

57
MECE 3345 Materials Science V. Diffusion in Solids

Fick’s First Law

dn
n2  n1  a v : Jump Frequency
n1 n2 dx
1
  : average tune if atome stay at the lattice site
v
1
Jump Frequency along x direction :
x 6
J  J12  J 21
 1 1 
a J  a n1  n2 
 6 6 
2 1 dn
 a
6 dx

58
MECE 3345 Materials Science V. Diffusion in Solids

Geometric Factor and Diffusion Coefficient

dn
J  D J  J12  J 21
dx

2 Lattice parameter
a
D 
 Average stay time at interstitial site

Diffusion constant Geometric factor

11 2
Einstein formula D   : jump distance
6
Simple cubic FCC BCC
a 
2
a 
3
a
1 2 2
 1 1
6  
12 8 59
MECE 3345 Materials Science V. Diffusion in Solids

Steady State Diffusion

Steady state: the state where the concentration profile does not change with time,
which means at any time the concentration at certain spot in space is a constant.
c

Fick’s first law:

concentration

B
dn
J  D
dx n: number density
x
Position
J

x
Position
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MECE 3345 Materials Science V. Diffusion in Solids

Fick’s Second Law

n1 n2

c
c

concentration
t2
concentration

t1 A A
A
B
B x

x x
Position x
J

x
Position
J12 J 21
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 MECE 3345 Materials Science V. Diffusion in Solids

Diffusion into a Semi-infinite Solid

t ≤ 0, before diffusion start t > 0, diffusion start

n(x) = n0, 0≤ x≤ ∞ n (x=0) = ns , n (x = ∞) = n0
A B A B

n
ns
t increases

concentration
ns ns
n0
t=0
n0 n0
0 0 0 x
x=0 x=∞ x=0 x=∞ Position
Solution to the Fick’s second law
Fixed surface concentration.
n x ( t )  n0  x 
 1  erf   , erf: Gaussian error function
ns  n0  2 Dt 

62
MECE 3345 Materials Science V. Diffusion in Solids

2 x  2
Error function erf  x    e d
 0

63
 Applications of Diffusion
• Furnace for heat treating
steel using carburization.
• Carburizing is the addition
of carbon to the surface of
low-carbon steels at
temperatures ranging from
1560°F to 1740°F.
• Hardening is achieved
when a high carbon
martensitic case with good
wear and fatigue resistance
is superimposed on a
tough, low-carbon steel
core.
• Case hardening or surface hardening is the
process of hardening the surface of a metal,
often a low carbon steel, by diffusing
elements into the material's surface, forming
a thin layer of a harder alloy.
• Carbon atoms diffuse into the iron lattice
atoms at the surface.
• This is an example of interstitial diffusion.
• The C atoms make iron (steel) harder.
 Diffusion in Ceramics
• Diffusion in ceramics happens through “Vacancy
mechanism”.
• Schottky defect should be present for diffusion of
foreign element inside the ceramics to occur.
• Since there is movement of ionic charges, a current
fellows through the ceramic material when external
electrical field is applied
 Diffusion in Polymers
• For polymeric materials, our interest is often in the
diffusive motion of small foreign molecules (e.g., O2,
H2O, CO2, CH4) between the molecular chains rather
than in the diffusive motion of chain atoms within
the polymer structure
APPLICATIONS
DIFFUSION IN SEMICONDUCTERS
APPLICATION OF NON STUDY STATE DIFFUSION
METHOD OF IMPURITY DOPING